JPH0663139B2 - Method for producing deodorant acrylic synthetic fiber - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a deodorant acrylic synthetic fiber having excellent wash resistance.

(Prior art) Conventional methods of deodorization and deodorization include masking offensive odors with aromatic substances, oxidative decomposition of offensive odors with oxidizing agents such as potassium permanganate, salts, nitric acid, sodium hydroxide, A method of neutralizing with a neutralizing agent such as sodium carbonate and a method of absorbing a bad odor with activated carbon are known. However, among these methods, the method using a masking agent has a drawback that it is rather uncomfortable in a place where a person stays for a long time, and the other methods by oxidative decomposition, neutralization, immobilization or adsorption have a large selectivity for malodorous substances. There was a drawback.

On the other hand, for textile products, the fiber contains an antibacterial agent,
Sanitary processing is known to prevent bad odors by preventing the growth of bacteria. However, since this method is an indirect method, it has a drawback that it has no effect on the malodor generated by factors other than the reproduction of bacteria. Also, JP-A-59-66
Japanese Patent Laid-Open Publication No. 2003-242242 discloses that a diluted solution of a deodorant active ingredient extracted mainly from the leaves of Camellia plants, especially tea trees, sakaki, and Sancha flowers is added to a textile product by squeezing, coating, or spraying. According to this method, since the deodorant component adheres to the surface of the fiber, there is a drawback that the deodorant active component is easily removed by washing with water or dry cleaning.

The present inventors have completed the present invention as a result of earnest research to improve the above drawbacks.

(Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing deodorant acrylic polymerized fibers which has excellent washing resistance and retains the fiber performance and texture of acrylic synthetic fibers as they are. There is.

(Means for Solving the Problem) The present invention relates to a deodorant active ingredient extracted from a Camellia plant in the gel-swelled fiber after stretching and washing with water when the acrylic synthetic fiber is produced by wet spinning. And a polyoxyethylene (n = 10 to 30) alkylphenyl phosphate and / or a salt thereof are applied to the emulsion, and then the mixture is dried and densified to produce a deodorant acrylic synthetic fiber. Is.

The polymer forming the acrylic synthetic fiber used in the present invention preferably contains at least 40% by weight of acrylonitrile and has a fiber-forming ability. That is, 40% by weight or more of acrylonitrile and other vinyl monomers,
For example, acrylic acid, methacrylic acid, or alkyl esters thereof, vinyl acetate, vinyl chloride, vinylidene chloride, sodium allylsulfonate, sodium methacrylsulfonate, sodium vinylsulfonate, sodium styrenesulfonate, etc. Examples thereof include those copolymerized at a ratio of not more than wt%.

In particular, a copolymer of vinyl monomer and sulfonic acid group-containing monomer of 80% by weight or more and 20% by weight or less of acrylonitrile, or a copolymer containing 20-60% by weight of vinyl chloride and / or vinylidene chloride and a sulfonic acid group-containing monomer. Coalescence is preferred. The acrylic polymer may contain a resin such as cellulose acetate, polystyrene, acrylonitrile-styrene copolymer, polyvinyl acetate copolymer, polyvinyl butyral, or the like. In particular, the acrylic polymer containing 2 to 30% by weight of cellulose acetate is preferable.

Solvents for the acrylic polymer used in the wet spinning of the present invention include organic and inorganic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone, aqueous zinc chloride solution, aqueous rhodan salt solution, concentrated nitric acid, and particularly wet type. An organic solvent that tends to generate many voids during spinning is preferred.

The polymer solution is wet-spun in an ordinary coagulation bath, washed with water to give a deodorant active ingredient to the gel-swelling acrylic fiber after desolvation, and then dried and densified to give the fiber a deodorant active ingredient. It is contained inside.

As the deodorant active ingredient of the present invention, halavanol, flavonols and many other organic polymer substances are mainly used. From the leaves of camellia plants, camphoraceae-valued leaves or dried products thereof to alcohol-based organic solvents, Kent-based compounds. Examples include those obtained by heat extraction with an organic solvent, water or a mixed solvent thereof, and the like. Examples of the extraction raw material include tea plants, mountain tea flowers, camellias, sakaki, camellia plants such as Hisaki, laurels,
Fresh leaves of camphoraceae plants such as cinnamon and camphor trees or dried products thereof are preferable. In particular, a fresh leaf of a tea plant of a Camellia plant or a dried product thereof is suitable because it is easily available and highly safe. The extracted and purified product is fixed as follows: UV absorption spectrum shows maximum absorption at 276 ± 2 mμ (1000 times aqueous solution), boiling point 180 ~ 200 ℃ (200 mmHg),
Moreover, the 20 wt% propylene glycol solution has a refractive index: ▲ n ²⁰ _D ▼ = 1.418 ± 0.02 Optical rotation: ▲ α ²⁰ _D ▼ = 0.007 ± 0.002 Specific gravity: ▲ d ²⁰ ₂₀ ▼ = 1.025 ± 0.02

The method of applying the deodorant active ingredient of the present invention is not particularly limited, but it is preferably applied by an aqueous solution containing propylene glycol or an emulsion containing a nonionic, anionic or cationic surfactant.

In particular, an emulsion containing polyoxyethylene (n = 10 to 30) alkylphenyl ether phosphate and / or a salt thereof is preferable in order to improve the deodorizing effect and prevent sticking during dry densification. Polyoxyethylene (n = 10 to 30) alkylphenyl ether phosphate and / or salt thereof means polyoxyethylene (n = 10 to 30) octylphenyl ether phosphate and polyoxyethylene (n = 10 to 30) nonyl. Phenyl ether phosphate, polyoxyethylene (n = 10 to 30) dodecyl phenyl ether phosphate, and soda salt of each,
Refers to potassium and ammonium salts.

The conditions for drying and densifying in the method of the present invention are not particularly limited, but when using a roller dryer, the surface temperature is
120 ° C to 160 ° C, and for dry heat drying, use a hot air dryer at 120 to 180 ° C. The drying time is preferably 1 minute to 7 minutes. Further, it is particularly preferable to add an oil agent for fibers after drying and densifying and to perform wet heat treatment at 100 to 135 ° C., since the washing resistance of the deodorant acrylic is improved and the spinning property and knitting property are significantly improved.

(Effects of the Invention) According to the method of the present invention, the fiber performance and texture of ordinary acrylic synthetic fibers are maintained as they are, and the deodorizing effect due to washing hardly decreases.

The fibers obtained by the present invention can be used by mixing with other fibers such as ordinary acrylic synthetic fibers, polyester, nylon, cotton, rayon, wool, etc., and have a deodorizing property, such as blankets, carpets and mats. Since it can be used for a wide range of purposes such as socks, sheets, and cotton fluff, it is of great industrial significance.

(Examples) The present invention will be specifically described below with reference to Examples.

In the examples, "(%)" means "% by weight".

Example 1 Extraction and purification from tea leaves, ultraviolet absorption spectrum of 277 mμ
(1000 times aqueous solution) shows maximum absorption, boiling point 180-200 ℃
(20 mmHg), refractive index ▲ n ²⁰ _D ▼ = 1.421, optical rotation ▲ α ²⁰ _D ▼ = 0.008, specific gravity ▲ d ²⁰ ₂₀ ▼ = 1.028, 20% propylene glycol solution of deodorant active ingredient in water Diluted to give a 5% solution.

AN / MA / SMAS = 90.7 / 8.5 / 0.8 acrylic polymer 90
2 parts of a 23% DMF solution of a mixed polymer of 10 parts and 10 parts of cellulose acetate.
Fibers in a gel swollen state after being subjected to normal drawing and water washing steps after being spun in a 50% DMF aqueous solution at 5 ° C were dried and densified at 150 ° C using a roller dryer after applying the above solution. Next, an oil agent for fibers was applied, mechanical crimping was applied, and then crimp setting was performed at 120 ° C. in wet heat.

A circular knit fabric was prepared from this fiber and a washing test was conducted to determine the trimethylamine removal rate after washing. For comparison,
A circular knitted fabric of ordinary acrylic fiber was impregnated with the above 5% solution, and then the dried circular knitted fabric was similarly subjected to the washing test.

As shown by the above results, the fibers applied in the gel swollen state had good washing resistance.

[Washing conditions]

Commercially available small electric machine Washing machine Neutral detergent 1 g / bath ratio 1: 100 Temperature x time 40 ° C x 5 minutes Water washing 10 minutes Dry 80 ° C x 1 hour [Trimethylamine removal rate measurement method] 350 cm ³ Sample in a closed container (35 cm X 20 cm) each, and 1 ml of 1% trimethylamine was added and the mixture was sealed. Then, after standing for 24 hours, 1 ml of headspace gas was taken and gas chromatographic analysis was performed. Similarly, a blank test (1% -trimethylamine 1 ml only) was carried out to determine the removal rate.

Example 2 Acrylonitrile (AN) / methyl acrylate (MA) /
Sodium methallyl sulfonate (SMAS) = 91.4 / 8.0 / 0.6 20% of acrylic polymer dimethylformamide (DM
F) The solution was spun into a 58% DMF aqueous solution at 20 ° C., and the gel-swelled fiber after the usual stretching and washing step was added to the 5% solution of the deodorant active ingredient obtained in Example 1 and polyoxy After applying a solution containing 1% of ethylene (n = 12) nonylphenyl ether phosphate potassium salt, the mixture was dried and densified at 140 ° C. using a roller dryer. Next, an oil agent for fibers was applied, mechanical crimping was applied, and then crimp setting was performed at a wet heat of 125 ° C.

A circular knit fabric was prepared from this fiber and washed in the same manner as in Example 1
As a result of obtaining the trimethylamine removal rate after 10 times and 5 times,
The washing resistance was 92.3% after 0 washes and 75.3% after 5 washes.

Example 3 24 of acrylic polymer having AN / vinylidene chloride (Vcl ₂ ) / sodium allyl sulfonate (SAS) = 56.0 / 4.20 / 2.0
% DMF solution was spun into a 55% DMF aqueous solution at 15 ° C. and subjected to a normal drawing and washing step to form a gel swollen fiber, and a 10% solution of the deodorant active ingredient similar to that in Example 1 was added to polyoxyethylene ( (n = 10) Octyl phenyl ether phosphate was added at 1%, and a solution adjusted to PH5 with caustic potash was administered, and then dried and densified at 145 ° C. using a roller dryer. Next, apply a normal fiber oil agent, apply mechanical crimp, and then moist heat.
Crimp setting was performed at 115 ° C.

A circular knitted fabric was prepared from this fiber, and the trimethylamine removal rate after 0 and 5 washings was determined in the same manner as in Example 1. As a result, it was found that good washing resistance was 97.8% after 0 washing and 80.4% after 5 washings. Indicated.

Comparative Example 2 Polyoxyethylene (n = 16) nonylphenyl ether sulfate soda salt 60%, ethoxydiglycol 40
A deodorant acrylic fiber was produced in the same manner as in Example 2 except that the emulsifier mixture (%) was used in addition to polyoxyethylene (n = 12) nonylphenyl ether phosphate potassium salt. However, the obtained fiber had tackiness and was inferior in spinnability as compared with Example 2.

Comparative Example 3 A deodorant acrylic fiber was produced in the same manner as in Example 2 except that iron ascorbate was used instead of the deodorant active ingredient extracted and purified from tea leaves. However, heat generated coloring of the fibers during the drying and densification process.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location D06M 13/295 // D06M 101: 28

Claims (1)

[Claims] 1. When producing acrylic synthetic fibers by wet spinning, deodorizing active ingredients and polyoxyethylene (n = 10) extracted from Camellia plants are added to the fibers in a gel-swelling state after stretching and washing with water. ~ 30) A method for producing a deodorant acrylic synthetic fiber, which comprises applying an emulsion containing an alkylphenyl ether phosphate and / or a salt thereof, and then performing dry densification.